CO2 Absorption Mechanism by the Deep Eutectic Solvents Formed by Monoethanolamine-Based Protic Ionic Liquid and Ethylene Glycol

Deep eutectic solvents (DESs) have been widely used to capture CO2 in recent years. Understanding CO2 mechanisms by DESs is crucial to the design of efficient DESs for carbon capture. In this work, we studied the CO2 absorption mechanism by DESs based on ethylene glycol (EG) and protic ionic liquid ([MEAH][Im]), formed by monoethanolamine (MEA) with imidazole (Im). The interactions between CO2 and DESs [MEAH][Im]-EG (1:3) are investigated thoroughly by applying 1H and 13 C nuclear magnetic resonance (NMR), 2-D NMR, and Fourier-transform infrared (FTIR) techniques. Surprisingly, the results indicate that CO2 not only binds to the amine group of MEA but also reacts with the deprotonated EG, yielding carbamate and carbonate species, respectively. The reaction mechanism between CO2 and DESs is proposed, which includes two pathways. One pathway is the deprotonation of the [MEAH]+ cation by the [Im]− anion, resulting in the formation of neutral molecule MEA, which then reacts with CO2 to form a carbamate species. In the other pathway, EG is deprotonated by the [Im]−, and then the deprotonated EG, HO-CH2-CH2-O−, binds with CO2 to form a carbonate species. The absorption mechanism found by this work is different from those of other DESs formed by protic ionic liquids and EG, and we believe the new insights into the interactions between CO2 and DESs will be beneficial to the design and applications of DESs for carbon capture in the future.


Introduction
Recently, deep eutectic solvents have attracted much attention because of their unique properties, including a negligible vapor pressure, non-flammability, ease of synthesis, and tailorable polarity, which make them a promising alternative to traditional organic solvents [1,2]. Most of DESs are obtained by mixing appropriate hydrogen bond donors (HBDs) and hydrogen bond acceptors (HBAs). The applications of DESs in many fields have been investigated so far, such as organic synthesis, extractions processes, catalytic reactions and electrochemistry [3][4][5][6]. Moreover, DESs have been widely studied as absorbents for CO 2 capture [7][8][9][10][11]. Among them, functional DESs which could chemically absorb CO 2 have received much attention because of their high capacities. The chemical absorption of CO 2 by DESs depends on the chemical reactions between CO 2 and functional groups of DESs [12][13][14][15][16]. Therefore, understanding the reaction mechanisms between CO 2 and functional groups of DESs is important to the design of efficient DESs for CO 2 capture.
Trivedi et al. studied the CO 2 absorption mechanism by DESs employing ethylenediamine (EDA) as an HBD [17] and the results indicated that a carbamate species was formed between the amine group of EDA and CO 2 . In our previous work, we found that CO 2 was attached to ethylene glycol (EG) with the formation of a carbonate species when CO 2 2 of 7 was captured by DESs consisting of azolide-based ILs and EG [18]. Zhang et al. studied the interactions between CO 2 and ternary DESs consisting of ionic liquid (IL) 1-butyl-3methylimidazolium chloride ([Bmim][Cl]), imidazole (Im), and super base 1,5-diazabicyclo [4.3.0] non-5-ene (DBN) [19]. The results indicated that CO 2 was bonded to the C 2 -position of the imidazolium ring of the cation [Bmim] + . Zeng et al. investigated the reaction pathway between CO 2 and DESs composed of protic IL 1,4,5]undec-7-ene imidazolate ([DBUH][Im]) and EG [20] and it was found that CO 2 reacted both with the anion [Im] − and EG. Another reaction mechanism between CO 2 and DESs consisting of ionic liquid 1-ethyl-3-methylimidazolium 2-cyanopyrrolide ([Emim] ) and EG was reported by Gurkan and co-authors [21], and the results revealed that CO 2 was attached to the anion [2-CNpyr]-, the imidazolium cation and EG, by forming carbamate, carboxylate and carbonate species, respectively.
In a recent paper, Mukesh et al. reported the CO 2 capture by DESs based on EG and protic ILs [22]. The protic ILs they used were obtained by mixing polyamines or monoethanolamine (MEA) with imidazole (Im). These DESs showed a high absorption capacity for CO 2 . The authors also investigated the reactions between CO 2 and the DESs used in their work. On the basis of the NMR and FTIR results, they believed that CO 2 was bonded to the amine group of polyamines or MEA, and EG or anion [Im] − did not react with CO 2 .
However, in our study, we found that CO 2 not only binds with the amine group but also reacts with EG in DESs (Scheme 1), suggesting the CO 2 absorption mechanism reported by Mukesh et al. is inaccurate [22]. The absorption mechanism found by this work is different from those of other DESs formed by protic ionic liquids and EG. For example, CO 2 [16]. However, the mechanism found by our work indicates that CO 2 binds to both the amino group on the cation [MEAH] + and EG, but CO 2 is not bonded to the anion [Im] − in [MEAH][Im]-EG (1:3) DESs. We believe that the findings of our work provide new insights about the interactions between CO 2 and DESs, which will be useful to design new, efficient DESs for carbon capture in the future.
was formed between the amine group of EDA and CO2. In our previous work, we found that CO2 was attached to ethylene glycol (EG) with the formation of a carbonate species when CO2 was captured by DESs consisting of azolide-based ILs and EG [18] [20] and it was found that CO reacted both with the anion [Im] − and EG. Another reaction mechanism between CO2 and DESs consisting of ionic liquid 1-ethyl-3-methylimidazolium 2-cyanopyrrolide ([Emim] ) and EG was reported by Gurkan and co-authors [21], and the results revealed that CO2 was attached to the anion [2-CNpyr]-, the imidazolium cation and EG by forming carbamate, carboxylate and carbonate species, respectively.
In a recent paper, Mukesh et al. reported the CO2 capture by DESs based on EG and protic ILs [22]. The protic ILs they used were obtained by mixing polyamines or monoethanolamine (MEA) with imidazole (Im). These DESs showed a high absorption capacity for CO2. The authors also investigated the reactions between CO2 and the DESs used in their work. On the basis of the NMR and FTIR results, they believed that CO2 was bonded to the amine group of polyamines or MEA, and EG or anion [Im] − did not reac with CO2.
However, in our study, we found that CO2 not only binds with the amine group bu also reacts with EG in DESs (Scheme 1), suggesting the CO2 absorption mechanism reported by Mukesh et al. is inaccurate [22]. The absorption mechanism found by this work is different from those of other DESs formed by protic ionic liquids and EG. For example, CO2 reacted both with the anion [Im] − and EG, but did not react with the cation [ [16]. However, the mechanism found by our work indicates that CO2 binds to both the amino group on the cation [MEAH] + and EG, but CO2 is not bonded to the anion [Im] − in [MEAH][Im]-EG (1:3) DESs. We believe that the findings of our work provide new insights about the interactions between CO2 and DESs, which will be useful to design new efficient DESs for carbon capture in the future.

Results and Discussion
At first, we prepared the DESs [MEAH][Im]-EG (1:3) following the procedures reported by Mukesh and co-authors [22]. The formation of [MEAH][Im] was confirmed by the 1 H NMR results ( Figure S1). As shown in Figure S1, the -NH3 + peak can be observed

Results and Discussion
At first, we prepared the DESs [MEAH][Im]-EG (1:3) following the procedures reported by Mukesh and co-authors [22]. The formation of [MEAH][Im] was confirmed by the 1 H NMR results ( Figure S1). As shown in Figure S1, the -NH 3 + peak can be observed at 5 Figure S2), which is similar to that reported by Mukesh's paper, and the diagram of the CO 2 absorption apparatus is shown in Figure S3. The 1 H ( Figure 1a) and 13 C (Figure 1b) NMR spectra of [MEAH][Im]-EG(1:3) before and after CO 2 capture were carefully studied. As shown in Figure 1a, the hydrogen peaks of -CH 2group (H-a and H-b ) of MEA-based carbamate can be found after CO 2 absorption, [23] suggesting the CO 2 is bonded to the amine group. However, two other new peaks at 3.05 (H-2) and 3.35 (H-3) ppm can also be found in Figure 1a. As seen in Figure 1b, the carbon signals of -CH 2 -group related to the MEA-based carbamate can be found at 42.7 (C-a ) and 60.6 (C-b ) ppm, and the carbonyl signal of MEA-based carbamate appears at 163.3 (C-e) ppm. However, there are three other new peaks at 60.7 (C-2), 65.9 (C-3), and 158.2 (C-4) ppm. the 13 C NMR spectra of [TEPA]2[Im]:EG-4 after CO2 absorp paper), the carbonyl carbon of EG-based carbonate appeared a our opinion, the 13 C NMR results of [TEPA]2[Im]:EG-4 after ca CO2 reacted with EG by forming carbonate species. Interesting peaks H-c, H-d, and H-1 shift slightly to upfield, and the H-a p carbon capture. These shifts may be due to the change in the h the DESs because of the formations of carbamate and carbonat In order to assign the new peaks in the 1 H and 13 C NMR spectra after CO 2 capture, the 1 H-13 C HMBC NMR spectra of [MEA][Im]-EG (1:3) after CO 2 capture were investigated ( Figure 2). As shown in Figure 2, C-e correlates with the H-a , suggesting the formation of the MEA-based carbamate. Moreover, the carbonyl carbon C-4 correlates with the H-3, and the correlation between C-4 and the hydrogens on the imidazole ring also could not be seen. The 1 H-13 C HMBC suggested that the carbon C-4 should be the carbonyl carbon of the carbonate formed by CO 2 and EG. The carbons at 60.7 (C-2) and 65.9 (C-3) ppm are the -CH 2 -carbons of HO-CH 2 -CH 2 -OCOO − [20,21]. Similar carbon peaks could also be found in the Mukesh and co-authors' paper [22]. As shown in Figure S4 of Mukesh and co-authors' paper, the -CH 2 -carbons of HO-CH 2 -CH 2 -OCOO − could be clearly observed in the 13 C NMR spectra of [TEPA] 2 [Im]:EG-4 after CO 2 absorption, which disappeared after CO 2 desorption. In Figure S10a of their paper, the -CH 2 -carbons of HO-CH 2 -CH 2 -OCOO − could also be found in the 13 C NMR spectra of TPEA-EG solution after CO 2 capture, and the carbonyl carbon of EG-based carbonate appeared at 159.67 ppm. In the 13 C NMR spectra of [TEPA] 2 [Im]:EG-4 after CO 2 absorption (Figure S10c of their paper), the carbonyl carbon of EG-based carbonate appeared at 159.79 ppm. Therefore, in our opinion, the 13 C NMR results of [TEPA] 2 [Im]:EG-4 after carbon capture indicated that CO 2 reacted with EG by forming carbonate species. Interestingly, as seen in Figure 1a, the peaks H-c, H-d, and H-1 shift slightly to upfield, and the H-a peak shift to downfield after carbon capture. These shifts may be due to the change in the hydrogen bonds network in the DESs because of the formations of carbamate and carbonate species after capture.   Figure S11 of their pap did not react with EG on the basis of the HMBC results, we not accurate because the 13 C peaks in the HMBC spectra ar the 13 C NMR spectra of Figure S10c of their paper. In the 13 C the carbamate signals were in the range of 164 to 165 ppm an was at 159.79 ppm. In their HMBC spectra, the carbamate s ppm, but the peak near 159 ppm could not be observed obtained may be incorrect.
Our findings were further confirmed by the FTIR s [MEAH][Im]-EG (1:3) before and after CO2 capture were sh 1635 cm −1 is associated with the combined C=O stretch carbamate species, and the peak at 1573 cm −1 corresponds to of carbamate -NHCOO − . The new peak at 1296 cm −1 is ascri Although Mukesh and co-authors investigated the HMBC spectra of [TEPA] 2 [Im]:EG-4 after CO 2 capture (Figure S11 of their paper) and they believed that CO 2 did not react with EG on the basis of the HMBC results, we think their HMBC results are not accurate because the 13 C peaks in the HMBC spectra are not consistent with those in the 13 C NMR spectra of Figure S10c of their paper. In the 13 C NMR spectra of Figure S10c, the carbamate signals were in the range of 164 to 165 ppm and the strong carbonate signal was at 159.79 ppm. In their HMBC spectra, the carbamate signals can be found near 165 ppm, but the peak near 159 ppm could not be observed, so the HMBC spectra they obtained may be incorrect.
Our findings were further confirmed by the FTIR spectra. The FTIR spectra of [MEAH][Im]-EG (1:3) before and after CO 2 capture were shown in Figure 3. The peak at 1635 cm −1 is associated with the combined C=O stretching band of carbonate and carbamate species, and the peak at 1573 cm −1 corresponds to COO − asymmetric stretching of carbamate -NHCOO − . The new peak at 1296 cm −1 is ascribed to the stretching band of RO-COO − [21]. The FTIR results suggested again that both carbonate and carbamate species are formed after CO 2 capture. carbamate species, and the peak at 1573 cm corresponds to COO asy of carbamate -NHCOO − . The new peak at 1296 cm −1 is ascribed to the RO-COO − [21]. The FTIR results suggested again that both carbon species are formed after CO2 capture.  [Im]-EG, which may be due to that DBU is a much stronger base than MEA. In other words, [DBUH] + is a much weaker acid than [MEAH] + , rendering the deprotonation of [DBUH] + by [Im] − extremely difficult, so CO 2 is not found to be bonded to DBU in the [DBUH][Im]-EG DESs after CO 2 capture [20]. In our previous work, the steric hindrance of functional groups is also found to be a factor that affects the CO 2 absorption mechanism. [24,25]. Therefore, we suggest that the factors, which may include the basicity, acidity, and the steric hindrance of functional groups of DESs, should be considered to modulate the CO 2 absorption mechanism by DESs.  [20]. In our previous work, the steric hindrance of functional groups is also found to be a factor that affects the CO2 absorption mechanism. [24,25]. Therefore, we suggest that the factors, which may include the basicity, acidity, and the steric hindrance of functional groups of DESs, should be considered to modulate the CO2 absorption mechanism by DESs.

Materials and Characterizations
Imidazole (Im, 98%), ethylene glycol (EG, 99.5%), and monoethanolamine (MEA, 99%) were obtained from J&K Scientific Ltd. (Beijing, China). CO 2 (≥99.99%) was supplied by Beijing ZG Special Gases Sci. and Tech. Co. Ltd. The 1 H NMR (600 MHz) and 13 C NMR (151 MHz) spectra were recorded on a Bruker spectrometer using DMSO-d 6 as an external solvent. FTIR spectra were recorded on a PerkinElmer Frontier spectrometer with an attenuated total reflection (ATR) accessory. The water content of the DESs was determined using Karl Fisher titration by V20 Volumetric KF titrator (Mettler Toledo, Zaventem, Belgium).

Synthesis of [MEAH][Im] and DESs
The procedure to prepare [

CO 2 Absorption
[MEAH][Im]-EG (1:3) (2.0 g) was added into a glass tube with a diameter of 10 mm. The tube was equipped with a rubber lid, which contained two needles. The tube was partially immersed in a water bath (25 ± 0.3 • C), and CO 2 was bubbled into the solvent through one needle at a flow rate of~50 mL/min, and the other needle was for a CO 2 outlet. The weight difference of the tube before and after CO 2 absorption was determined by an electronic balance (±0.1 mg).

Conclusions
The reaction mechanism between CO 2 and DES [MEA][Im]-EG (1:3) is studied carefully by using NMR and FTIR spectroscopy. The CO 2 capacity of [MEA][Im]-EG (1:3) is 8.94 wt% at 25 • C and 1.0 atm. The results indicate that CO 2 not only binds with the amino group of MEA but also reacts with the deprotonated EG in the solvent. There are two possible reaction pathways that form carbamate and carbonate species. One is the deprotonation of the [MEAH] + cation by [Im] − anion, forming the neutral molecule MEA, which then reacts with CO 2 to form a carbamate species. Another one is the reaction between EG and [Im] − , forming the HO-CH 2 -CH 2 -O − anion, which then binds with CO 2 to form a carbonate species. We believe the new insights about the interactions between CO 2 and DESs will bring benefits to the design and applications of DESs for carbon capture in the future.